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CHAPTER 23

THE TRANSITION ELEMENTS


PRACTICE EXAMPLES
1A

1B

(E) (a) Cu 2 O should form.


(b)

W(s) is the reduction product.

(c)

Hg(l) forms.

2 Cu 2S s + 3 O 2 g 2 Cu 2 O s + 2 SO 2 g

WO3 s + 3 H 2 g W s + 3 H 2 O g

2 HgO s
2 Hg l + O 2 g

(E) (a) SiO 2 s is the oxidation product of Si.

3 Si s + 2 Cr2 O3 s
3 SiO 2 s + 4 Cr s

(b)
(c)
2A

, Air
Co 2 O3 s + 3H 2 O g
Roasting is simply heating in air. 2 Co OH 3 s

MnO 2 s forms; (acidic solution). Mn 2+ aq + 2H 2 O(l) MnO 2 s + 4H + aq + 2e

(M) We write and combine the half-equations for oxidation and reduction. If E o 0 , the
reaction is spontaneous.

Oxidation: {V 3+ aq + H 2 O(l) VO 2+ aq + 2H + aq + e } 3

E o = 0.337V

Reduction: NO3 aq + 4H + aq + 3e NO g + 2H 2 O

E o = +0.956V

Net: NO3- aq + 3V 3+ aq + H 2 O(l) NO g + 3VO 2+ aq + 2H + aq

Ecell o = +0.619V

Because the cell potential is positive, nitric acid can be used to oxidize V 3+ aq to VO 2+ aq
under standard conditions.
2B

(M) The reducing couple must have a half-cell potential of such a size and sign that a positive
sum results when this half-cell potential is combined with
E o {VO 2 (aq)|V 2 (aq)} 0.041V (this is the weighted average of the VO2+ | V3+ and V3+ | V2+
reduction potentials) and a negative sum must be produced when this half-cell potential is
combined with E o {V 2 (aq)|V(s)}= 1.13V .

So, -Eo for the couple must be > 0.041 V and < + 1.13 V (i.e., it cannot be more positive than
1.13V, nor more negative than 0.041 V). Some possible reducing couples from Table 20-1 are:
E o {Cr 3 (aq)|Cr 2+ (aq)} 0.42 V ; E o {Fe 2+ (aq)|Fe(s)} 0.440 V
E o {Zn 2+ (aq)|Zn(s)} 0.763 V . Thus Fe(s), Cr2+(aq), and Zn(s) will do the job.

INTEGRATIVE EXAMPLE
3A

(M) Because the reduction potential for PtCl62 is more positive than that of V3+, the
following half-reactions occur spontaneously in the cell:
E = +0.255 V
Oxidation: [ V2+ + e V3+ ] 2
2
2

E = +0.68 V
Reduction: PtCl6 + 2 e PtCl4 + 2 Cl
Overall: 2 V2+ + PtCl62 2 V3+ + PtCl42 + 2 Cl E = 0.94 V
1136

Chapter 23: The Transition Elements

2(0.94)
The equilibrium constant for the overall reaction is K 10 0.0592 5.7 1031 . For the
reverse reaction to be spontaneous, we need Q > 5.7 1031. Because Q = [V3+]2 [PtCl42]
[Cl]2/[V2+] [PtCl62], the formation of PtCl62 is favored by using a very low
concentration of V2+ and very high concentrations of V3+, PtCl42, and Cl. In practical
terms, though, the amount of PtCl62 that could be formed spontaneously would be small.
A quick calculation shows that starting from [V3+]o = [PtCl42]o = [Cl]o = 1. M and [V2+]
= [PtCl62]o = 0, the equilibrium concentration of PtC62 would be about 1.6 1011 M.
So, in practical terms, an external voltage source would be required to make a significant
amount of PtCl62 from V3+, PtCl42, and Cl.

3B
(M) The disproportionation reaction is 3 Ti2+ 2 Ti3+ + Ti and E = 1.261 V. Because
E < 0, the reaction is not spontaneous under standard conditions.

EXERCISES
Properties of the Transition Elements
1.

(E) (a) Ti

[Ar]

3d

4s

(b)

V 3+ [Ar]

3d

4s

2.

(c)

Cr 2+

[Ar]

3d

4s

(d)

Mn 4+ [Ar]

3d

4s

(e)

Mn 2+

[Ar]

3d

4s

(f)

Fe 3+

3d

4s

[Ar]

(E) We first give the orbital diagram for each of the species, and then count the number
of unpaired electrons.

Fe

[Ar]

3d

4s

4 unpaired electrons

Sc 3+

[Ar]

3d

4s

0 unpaired electrons

Ti 2+

[Ar]

3d

4s

2 unpaired electrons

Mn 4+

[Ar]

3d

4s

3 unpaired electrons

Cr

[Ar]

3d

4s

6 unpaired electrons

Cu 2+

[Ar]

3d

4s

1 unpaired electron

Finally, arrange in order of decreasing number of unpaired e-: Cr Fe Mn 4+ Ti 2+ Cu 2+ Sc 3+


3.

(M) A given main-group metal typically displays just one oxidation state, usually equal to
its family number in the periodic table. Exceptions are elements such as Tl ( +1 and +3 ), Pb

1137

Chapter 23: The Transition Elements

( +2 and +4 ), and Sn ( +2 and +4 ), for which the lower oxidation state represents a pair of s
electrons not being ionized (a so-called inert pair).
Main group metals do not form a wide variety of complex ions, with Al3+ , Sn 2+ , Sn 4+ , and
Pb 2+ being major exceptions. On the other hand, most transition metal ions form an extensive
variety of complex ions. Most compounds of main group metals are colorless; exceptions
occur when the anion is colored. On the other hand, many of the compounds of transition
metal cations are colored, due to d-d electron transitions. Virtually every main-group metal
cation has no unpaired electrons and hence is diamagnetic. On the other hand, many transition
metals cations have one or more unpaired electrons and therefore are paramagnetic.
4.

(M) As we proceed from Sc to Cr, the valence electron configuration has an increasing
number of unpaired electrons, which are capable of forming bonds to adjacent atoms. As we
continue beyond Cr, however, these electrons become paired, and the resulting atoms are less
able to form bonds with their neighbors. Also, smaller atoms tend to bond more tightly,
making their metallic agglomerations more difficult to melt. (i.e., the smaller the metal atom,
the higher the melting point). This trend of increasing melting point with decreasing size is
clearly visible for the first transition series from Sc to Zn.

5.

(M) When an electron and a proton are added to a main group element to create the element of
next highest atomic number, it is the electron that influences the radius. The electron is added to
the outermost shell (n value), which is farthest from the nucleus. Moreover, the added electron
is well shielded from the nucleus and hence it is only weakly attracted to the nucleus. Thus, this
electron billows out and, as a result, has a major influence on the size of the atom. However,
when an electron and a proton are added to a transition metal atom to create the atom of next
highest atomic number, the electron it is not added to the outermost shell. The electron is added
to the d-orbitals, which are one principal quantum number lower than the outermost shell. Also,
the electron in the same subshell as the added electron offers little shielding. Thus it has small
effect on the size of the atom.

6.

(M) The reason why the radii of Pd (138 pm) and Pt (139 pm) are so similar, and yet so
different from the radius of Ni (125 pm) is because the lanthanide series intrudes between
Pd and Pt. Because of the lanthanide contraction, elements in the second transition row are
almost identical in size to their congeners (family members) in the third transition row.

7.

(M) Of the first transition series, manganese exhibits the greatest number of different
oxidation states in its compounds, namely, every state from +1 to +7 . One possible
explanation might be its 3d 5 4 s2 electron configuration. Removing one electron produces an
electron configuration ( 3d 5 4 s1 ) with two half-filled subshells, removing two produces one
with a half-filled and an empty subshell. Then there is no point of semistability until the
remaining five d electrons are removed. These higher oxidation states all are stabilized by
being present in oxides ( MnO 2 ) or oxoanions (e.g., MnO4 ).

8.

(M) At the beginning of the series, there are few electrons beyond the last noble gas that
can be ionized and thus the maximum oxidation state is limited. Toward the end of the
series, many of the electrons are paired up or the d subshell is filled, and thus a somewhat
stable situation would be disrupted by ionization.

1138

Chapter 23: The Transition Elements

9.

(M) The greater ease of forming lanthanide cations compared to forming transition metal
cations, is due to the larger size of lanthanide atoms. The valence (outer shell) electrons of
these larger atoms are further from the nucleus, less strongly attracted to the positive charge
of the nucleus in diffuse f-orbitals that are do not penetrate effectively and are very
effectively shielded by the core electrons. As a result, they are removed much more readily.

10.

(M) This is not a simple straightforward question. There are a number of factors to consider.
Proceeding across the first transition series, electrons are added to the 3d subshell which is a
shell that is beneath the 4s subshell, the outer most subshell in the valence shell occupied by
one or two electrons. The metallic character of the first transition element, Sc, is rather similar
to that of Ca (e.g., E = 2.03 V compared to 2.84 V). Following this, there is a fairly regular
rise in E, (e.g., 1.63 V for Ti , 1.13 V for V), reaching a maximum of E = 0.340 V with
Cu. These trends can be related to the regular increase in Zeff and other aspects of electron
configurations (half filled shell for Mn2+ and loss of half filled shell for Cr2+). Complicating
matters is the fact that these ions will have different aqueous coordination numbers and
geometries.

In the lanthanide series, it is the 4f subshell that fills at the same time that the 5d subshell is
mostly vacant and the 6s subshell is filled. Differences in electron configurations are
essentially confined to a subshell two shells removed from the outermost valence shell, which
translates into close similarities among all the elements in the series, including E values.
Recall that the lanthanide series is an inner transition seriesa transition series within another
transition series. This inner transition series runs its course between La (E = 2.38 V) and Hf
(E = 1.70 V). The difference between these two E values is about 0.7 V, which is comparable
to the 0.4 V difference between the first (Sc) and second (Ti) members of the first transition series.

Reactions of Transition Metals and Their Compounds


11.

12.

(M) (a) TiCl4 g + 4 Na l


Ti s + 4NaCl l

(b)

Cr2 O3 s + 2Al s
2 Cr l + Al2 O3 s

(c)

Ag s + HCl aq no reaction

(d)

K 2 Cr2 O7 aq + 2KOH aq 2 K 2CrO 4 aq + H 2 O(l)

(e)

MnO 2 s + 2 C s
Mn l + 2CO g

(M) (a) Cr s + 2HCl aq CrCl2 aq + H 2 g


metal except Cu can be substituted for Cr.
(b)

Virtually any first period transition

Cr2 O3 s + 2 OH aq + 3 H 2 O(l) 2 Cr OH 4 aq

The oxide must be amphoteric. Thus, Sc 2 O3 , TiO 2 , ZrO 2 , and ZnO could be
substituted for Cr2 O3 .

1139

Chapter 23: The Transition Elements

(c)

2 La s + 6 HCl aq 2 LaCl3 aq + 3 H 2 g

Any lanthanide or actinide element can be substituted for lanthanum.


13.

14.

15.

(M) (a) Sc OH 3 s + 3H + aq Sc3+ aq + 3 H 2 O(l)


(b)

3 Fe 2+ aq + MnO 4 aq + 2 H 2 O l 3 Fe3+ aq + MnO 2 s + 4 OH (aq)

(c)

2 KOH l + TiO 2 s
K 2 TiO3 s + H 2 O g

(d)

Cu s + 2 H 2SO 4 conc, aq CuSO 4 aq + SO 2 g + 2 H 2 O(l)

electrolysis
(M) (a) 2 Sc 2 O3 l,in Na 3ScF6 + 3 C s
4 Sc l + 3 CO 2 g

(b)

[By analogy with the equation for the electrolytic production of Al]
Cr s + 2 HCl aq Cr 2+ aq + 2 Cl aq + H 2 g

(c)

4 Cr 2+ aq + O 2 g + 4 H + aq 4 Cr 3+ aq + 2 H 2 O(l)

(d)

Ag s + 2 HNO3 aq AgNO3 aq + NO 2 g + H 2 O(l)

(M) We write some of the following reactions as total equations rather than as net ionic
equations so that the reagents used are indicated.
(a)

FeS s + 2 HCl aq FeCl2 aq + H 2S g

4 Fe 2+ aq + O 2 g + 4H + aq 4Fe3+ aq + 2 H 2 O(l)
Fe3+ aq + 3 OH aq Fe OH 3 s
(b)

BaCO3 s + 2 HCl aq BaCl2 aq + H 2 O(l) + CO 2 g


2 BaCl 2 aq + K 2 Cr2 O 7 aq + 2 NaOH aq 2 BaCrO 4 s + 2 KCl aq + 2 NaCl aq + H 2 O(l)

16.

(M) (a) (i) CuO s 2H (aq)


Cu 2+ aq + H 2 O l
(ii) Cu 2+ aq 2OH (aq)
Cu(OH) 2 s
(b)

N 2 g + 4 H 2 O g + Cr2 O3 s
NH 4 2 Cr2O7 s

Cr2 O3 s + 6 HCl aq CrCl3 aq + 3 H 2 O(l)

Extractive Metallurgy
17.

(E) HgS(s) + O2(g)


Hg(l) + SO2(g)

4 HgS(s) + 4 CaO(s)
4 Hg(l) + 3 CaS(s) + CaSO4(s)

18.

(E) (a) C(s) + O2(g) CO2(g)


S = 213.7 J K-1 - (5.74 J K-1 + 205.1 J K-1)
S = 2.86 J K-1

Since S 0, G will be relatively constant with temperature.

1140

Chapter 23: The Transition Elements

(b)

19.

S = (2(213.7 J K-1) - (205.1 J K-1 + 2(197.7 J K-1))


S = -173.1 J K-1
Since S is less than zero, G will increase (become less negative or more positive) as
temperature increases.

2 CO(g) + O2(g) 2 CO2(g)

(M) The plot of Go versus T will consist of three lines of increasing positive slope.
The first line is joined to the second line at the melting point for Ca(s), while the second
line is joined to the third at the boiling point for Ca(l).

2 Ca(s) + O2(g) 2 CaO(s) Hf = -1270.2 kJ


S = 2(39.75 J K-1) [2(41.42 J K-1) + 205.1 J K-1] = -208.4 J K-1

The graph should be similar to that for 2 Mg(s) + O2(g) 2 MgO(s). We expect a
positive slope with slight changes in the slope after the melting point (839 C) and boiling
point (1484 C) , mainly owing to changes in entropy. The plot will be below the
G line for 2 Mg(s) + O2(g) 2 MgO(s) at all temperatures.
20.

(E) 2 Na2CrO4(s) + 3 C(s) + 4HCl(aq) Cr2O3(s) + 2H2O(l) + 3 CO(g) + 4NaCl(aq)

2 Cr2O3(s) + 3 Si(s) 4 Cr(s) + 3 SiO2(s)

Oxidation-Reduction
21.

(E) (a) Reduction:


(b)

22.

(E) (a) Oxidation:


(b)

23.

Oxidation:

Reduction:

VO 2+ aq + 2H + aq + e V3+ aq + H 2O (l)

Cr 2+ aq Cr 3+ aq + e

Fe OH 3 s + 5 OH aq FeO4

aq + 4 H 2O(l) + 3e

Ag CN 2 aq + e Ag s + 2 CN aq
2

(M) (a) First we need the reduction potential for the couple VO+2 aq / V2 + aq . We will
use the half-cell addition method learned in Chapter 20.

VO 2 aq + 2 H + aq + e VO 2+ aq + H 2 O(l)

G o = 1 F +1.000 V

VO 2+ aq + 2 H + aq + e V 3+ aq + H 2 O(l)

G o = 1 F +0.337 V

V 3+ aq + e V 2+ aq

G o = 1 F 0.255 V

VO 2 aq + 4 H + aq + 3 e V 2+ aq + 2 H 2 O

G o = 3 FE o

Eo =

1.000 V + 0.337 V 0.255 V


= + 0.361 V
3

1141

Chapter 23: The Transition Elements

We next analyze the oxidation-reduction reaction.


Oxidation: {2 Br aq Br2 l + 2e } 3

E o = 1.065 V

Reduction: {VO 2 + aq + 4H + aq + 3e V 2+ aq + 2H 2 O(l)} 2 E o = +0.361V


Net: 6 Br aq + 2 VO 2 aq + 8 H + aq 3 Br2 l + 2 V 2+ aq + 4 H 2 O
+

o
Ecell
= 0.704V
Thus, this reaction does not occur to a significant extent as written under standard
conditions.

(b)

Oxidation: Fe 2+ aq Fe3+ aq + e
Reduction: VO 2 aq + 2 H + aq + e VO 2+ aq + H 2 O(l)
+

Net:

E o = 0.771V

E o = +1.000V

Fe2+ aq + VO 2 aq + 2 H + aq Fe3+ aq + VO 2+ aq + H 2 O(l)


+

o
Ecell
= +0.229V
This reaction does occur to a significant extent under standard conditions.

(c)

Oxidation: H 2 O 2 2 H + aq + 2 e + O 2 g

E o = 0.695 V

Reduction: MnO 2 s + 4 H + aq + 2 e Mn 2+ aq + 2 H 2O(l)

E o = +1.23V

Net: H 2 O 2 + MnO 2 s + 2 H + aq O 2 g + Mn 2+ aq + 2 H 2 O(l)

Ecell = +0.54V

Thus, this reaction does occur to a significant extent under standard conditions.
24.

(D) When a species acts as a reducing agent, it is oxidized. From Appendix D, we obtain
the potentials for each of the following couples.

E 0 {Zn 2 (aq) / Zn(s)} 0.763V; E 0 {Sn 4 (aq) / Sn 2 (aq)} 0.154V


E o {I 2 (s)/I (aq)} = 0.535 V
Each of these potentials is combined with the cited reduction potential. If the resulting
o
value of Ecell
is positive, then the reducing agent will be effective in accomplishing the
desired reduction, which we indicate with yes; if not, we write no.
(a)

E o {Cr2 O7 (aq) / Cr 3 (aq)} = +1.33 V


2

o
Ecell
= E o {Cr2 O7 (aq) / Cr 3 (aq)} E o {Zn 2 (aq) / Zn(s)}
o
Ecell
= +1.33 V + 0.763 V = +2.09 V Yes

o
Ecell
= E o {Cr2 O7 (aq) / Cr 3 (aq)} E o {Sn 4 (aq) / Sn 2+ (aq)}
o
Ecell
= +1.33 V 0.154 V = +1.18 V Yes
2

o
Ecell
= E o {Cr2O7 (aq) / Cr 3 (aq)} E o {I 2 (s) / I (aq)}
o
Ecell
= +1.33 V 0.535 V = +0.80 V Yes

1142

Chapter 23: The Transition Elements

(b)

E o {Cr 3+ (aq)/Cr 2+ (aq)} = 0.424 V


o
Ecell
= E o {Cr 3+ (aq)/Cr 2+ (aq)} E o {Zn 2+ (aq)/Zn(s)}
o
Ecell
= 0.424 V + 0.763 V = +0.339 V Yes
o
Ecell
= E o {Cr 3+ (aq)/Cr 2+ (aq)} E o {Sn 4+ (aq)/Sn 2+ (aq)}
o
Ecell
= 0.424 V 0.154 V = 0.578 V No
o
Ecell
= E o {Cr 3+ (aq)/Cr 2+ (aq)} E o {I 2 (s)/I (aq)}
o
Ecell
= 0.424 V 0.535 V = 0.959 V No

(c)

E o {SO 4 (aq)/SO 2 (g)} = +0.17 V


2

o
Ecell
= E o {SO 4 (aq)/SO 2 (g)} E o {Zn 2+ (aq)/Zn(s)}
o
Ecell
== +0.17 V + 0.763 V = +0.93 V Yes
o
Ecell
= E o {SO 4 2 (aq)/SO 2 (g)} E o {Sn 4+ (aq)/Sn 2+ (aq)}
o
Ecell
= +0.17 V 0.154 V = +0.02 V

Yes (barely)

o
Ecell
= E o {SO 4 (aq)/SO 2 (g)} E o {I 2 (s)/I (aq)}
o
Ecell
= +0.17 V 0.535 V = 0.37 V

25.

No

(M) The reducing couple that we seek must have a half-cell potential of such a size and
sign that a positive sum results when this half-cell potential is combined
with E o {VO 2 (aq)|V 3 (aq)} 0.337 V and a negative sum must be produced when this
+

half-cell potential is combined with E o {V 3 (aq)|V 2 (aq)}= 0.255V .


So, -Eo for the couple must be> 0.337 V and <+ 0.255 V (i.e. it cannot be more
positive than 0.255V, or more negative than 0.337 V)
Some possible reducing couples from Table 20.1 are:
E o {Sn 2 (aq)|Sn(s)} 0.137 V ; E o {H + (aq)|H 2 (g)] 0.000 V
E o {Pb 2+ (aq)|Pb(s)] 0.125 V ; thus Pb(s), Sn(s), H2(g) , to name but a few, will do the job.
26.

(M) There are two methods that can be used to determine the MnO4-/Mn2+ reduction potential.
Method 1:
MnO4 1.70 V MnO2 1.23 V Mn2+

EMnO4-/ Mn2+ =

3 (1.70 V) + 2 (1.23 V)
= 1.512 V ~1.51 V
5

Method 2: MnO4- MnO42 MnO2 Mn3+ Mn2+


0.56 V + 2 (2.27 V) + 0.95 V +1.49 V
= 1.508 V ~1.51 V
5
These answers compare favorably to Table 20.1, where EMnO4-/ Mn2+ = 1.51 V
EMnO4-/ Mn2+ =

1143

Chapter 23: The Transition Elements

27.

(M) Table D-4 contains the following data: Cr 3+ /Cr 2+ reduction potential = -0.424 V,
Cr2 O7 2- /Cr 3+ reduction potential = 1.33 V and Cr 2+ /Cr reduction potential = -0.90 V.
By using the additive nature of free energies and the fact that G = -nFE, we can
determine the two unknown potentials and complete the diagram.
3(1.33V) - 0.424 V
Cr2 O7 2- /Cr 2+ : E =
= 0.892 V
(i)
4

(ii)

28.

Cr 3+ /Cr : E =

0.424 V + 2(-0.90 )V
= 0.74 V
3

(M) From Table 23.4 we are given: VO2+/VO2+ reduction potential = 1.000 V, VO2+/V3+
reduction potential = 0.337 V, V3+/V2+ reduction potential = -0.255 V and V2+/V reduction
potential = -1.13 V. By taking advantage of the additive nature of free energies and the fact that
G = -nFE, we can determine the three unknown potentials and complete the diagram.

(i)
(ii)
(iii)

1.000 V + 0.337 V
= 0.669 V
2
1.000 V + 0.337 V + (-0.255 V)
= 0.361 V
VO2+/V2+: E =
3
1.000 V + 0.337 V + (-0.255 V) + 2(-1.13 V)
VO2+/V: E =
= 0.24 V
5

VO2+/V3+: E =

Chromium and Chromium Compounds


29.

(M) Orange dichromate ion is in equilibrium with yellow chromate ion in aqueous
solution.
2CrO 4 2 aq + 2H + aq
Cr2 O7 2 aq + H 2 O(l)

The chromate ion in solution then reacts with lead(II) ion to form a precipitate of yellow
PbCrO 4 s
lead(II) dichromate. Pb 2+ aq + CrO 4 2 aq
PbCrO 4 s will form until H + from the first equilibrium increases to the appropriate
level and both equilibria are simultaneously satisfied.
30.

(M) The initial dissolving reaction forms orange dichromate ion.


2 Ba 2+ aq + Cr2 O7 2 aq + 2 Cl aq + H 2 O(l)
2 BaCrO 4 s + 2 HCl aq

Dichromate ion is a good oxidizing agent, that is strong enough to oxidize Cl aq to


Cl2 g if the concentrations of reactants are high, the solution is acidic, and the product
Cl2 g is allowed to escape.
3Cl2 g + 2Cr 3+ aq + 7H 2 O(l)
6Cl aq + Cr2 O7 2 aq +14H + aq

1144

Chapter 23: The Transition Elements

Chromium(III) can hydrolyze in aqueous solution to produce green Cr OH 4 aq , but


the solution needs to be alkaline (pH >7) for this to occur. A more likely source of the
green color is a complex ion such as Cr H 2 O 4 Cl2 .
+

31.

(D) Oxidation: {Zn s Zn 2+ aq + 2e } 3

Reduction: Cr2 O 7

aq, orange +14H + aq + 6e 2 Cr 3+ aq, green + 7 H 2O(l)

3 Zn s + Cr2 O7

Net:
Oxidation:

aq +14 H + aq 3 Zn 2+ aq + 2 Cr 3+ aq + 7 H 2O(l)

Zn s Zn 2 + aq + 2e

Reduction:

{Cr 3+ aq,green + e Cr 2 + aq, blue }

Net:

Zn s + 2 Cr 3+ aq Zn 2+ aq + 2 Cr 2+ aq

The green color is most likely due to a chloro complex of Cr3+, such as Cr H 2 O 4 Cl2 .
+

32.

Oxidation:

{Cr 2+ aq, blue Cr 3+ aq,green + e }

Reduction:

O 2 g + 4 H + aq + 4e 2 H 2 O(l)

Net:

4 Cr 2+ aq + O 2 g + 4 H + aq 4 Cr 3+ aq + 2 H 2 O(l)

(M) CO 2 g , as the oxide of a nonmetal, is an acid anhydride. Its function is to make the
solution acidic. A reasonable guess of the reactions that occur follows.
Cr2O7 2 aq + H 2O(l)
2 CrO 4 2 aq + 2 H + aq
2H + aq + 2 HCO3 aq
2 H 2 O(l) + 2CO2 aq
Cr2 O7 2 aq + 2 HCO3 aq
2 CrO 4 2 aq + 2 CO 2 aq + H 2 O(l)

33.

2
(M) Simple substitution into Equation (23.19) yields Cr2 O7 in each case. In fact, the
expression is readily solved for the desired concentration as follows:
2

Cr2 O7 2 = 3.2 1014 H + CrO 4 2 . In each case, we use the value of pH to determine

+
pH
H = 10 .

(a)
(b)

Cr2O7 2 = 3.2 1014 (106.62 ) 2 (0.20) 2 0.74 M

2
2
Cr2O 7 = 3.2 1014 108.85 0.20 2 = 2.6 105 M

1145

Chapter 23: The Transition Elements

34.

(M) We use Equation (23.19) again:.

Cr2 O 27
2
= 3.2 1014 H + = 3.2 1014 10 7.55
2 2
CrO 4

CrO 4

initial
2

= 3.2 10 2.8 10 = 0.254


2

8 2

14

1.505 g Na 2 CrO 4 1 mol Na 2CrO 4


1 mol CrO 4
=
= 0.0269 M

0.345 L soln
161.97 g Na 2 CrO 4 1mol Na 2 CrO 4

Reaction:

2CrO 4 2 aq

Initial:
Changes:
Equil:

0.0269 M

2.8 108 (fixed)


0

2 x M

0.0269 2 x

2H + aq

Cr2O 27 aq + H 2 O (l)
0M

2.8 10 (fixed)

Cr2 O7 2
x

= 0.254 =
2
2 2
0.0269 2 x
CrO 4

x = 0.000184 0.0274 x +1.016 x 2

+x M
xM

x = 0.254 0.000724 0.108 x + 4 x 2

1.016 x 2 1.0274 x + 0.000184 = 0

b b 2 4ac 1.0274 1.0556 0.000736


=
= 1.0111 M, 0.00016 M
2a
2.032
We choose the second root because the first root gives a negative CrO 4 2 .
x=

Cr2O7 2 = x = 0.00016 M

CrO 4 2 = 0.0269 2 x = 0.0266 M

We carry extra significant figures to avoid a significant rounding error in this problem.
35.

(E) Each mole of chromium metal plated out from a chrome plating bath (i.e., CrO3 and
H2SO4) requires six moles of electrons.
3600 s 3.4 C 1 mol e 1 mol Cr 52.00 g Cr
= 1.10 g Cr

mass Cr =1.00 h
1 hr
1s
96485 C 6 mol e 1mol Cr

36.

(M) First we compute the amount of Cr(s) deposited.

1 cm
104 cm 2 7.14 g Cr 1 mol Cr
2
mol Cr = 0.0010 mm
= 5.1 102 mol Cr
0.375 m

2
3
10 mm
1 m 1 cm Cr 52.0 g Cr

Recall that the deposition of each mole of chromium requires six moles of electrons. We
now compute the time required to deposit the 5.1102 mol Cr .
6 mol e 96485 C 1s
1h
time = 5.1102 mol Cr
= 2.3 h

1 mol Cr 1mol e
3.5C 3600s
37.

(M) Dichromate ion is the prevalent species in acidic solution. Oxoanions are better
oxidizing agents in acidic solution because increasing the concentration of hydrogen ion
favors formation of product. The half-equation is:
Cr2 O72-(aq) 14 H (aq) 6 e
2 Cr 3 (aq) 7H 2O(l) Note that precipitation occurs

1146

Chapter 23: The Transition Elements

most effectively in alkaline solution. In fact, adding an acid to a compound is often an


effective way of dissolving a water-insoluble compound. Thus, we expect to see the form
that predominates in alkaline solution to be the most effective precipitating agent. Notice
2
2
also that CrO 4 is smaller than is Cr2 O7 , giving it a higher lattice energy in its
compounds, which makes these compounds harder to dissolve.
38.

(M) Both metal ions precipitate as hydroxides when OH is moderate.


Mg 2+ aq + 2 OH aq Mg OH 2 s

Cr 3+ aq + 3 OH aq Cr OH 3 s

Because chromium(III) oxides and hydroxides are amphoteric (and those of magnesium
ion are not), Cr OH 3 s will dissolve in excess base.

Cr OH 3 s + NaOH aq Na + aq + Cr OH 4 aq

The Iron Triad


39.

(M) 4 Fe2+(aq) + O2(g) + 4 H+ 4 Fe3+(aq) + 2 H2O(l)

E = 0.44 V

[Fe2+] = [Fe3+]; pH = 3.25 or [H+] = 5.6 10-4 and PO2 = 0.20 atm

0.0592
[Fe3+ ]4
log 2+ 4 + 4
E = E [Fe ] [H ] PO
n

[Fe3+ ]4
0.0592

log
= 0.44 V 2+ 4
-3.25 4

4
[Fe
]
[10
]
0.20

E = 0.24 V (spontaneous under these conditions)


40.

(M) {NiO(OH)(s) + e + H+(aq) Ni(OH)2(s)


{Cd(s) + 2 OH (aq) Cd(OH)2(s) + 2 e }1
{H2O(l) H+(aq) + OH-(aq)}
}2

}2
Eox

Ered

2 NiO(OH)(s) + Cd(s) + 2 H2O(l) Cd(OH)2(s) + 2 Ni(OH)2(s) Ecell 1.50 V


Eox may be obtained by combining the Ksp value for Cd(OH)2(s)
(K sp Cd(OH)2 2.5 1014 ) and Ered = -0.403 V for Cd2+(aq) + 2 e- Cd(s). Hence,

Cd(s) Cd2+(aq) + 2 e

Eox = 0.403 V

1
= 0.403 V
Cd (aq) + 2 OH (aq) Cd(OH)2(s) Ecell = 0.0592 log 1 = 0.0592 log
-14
K
n
2
2.5
10

sp
2+

Cd(s) + 2 OH-(aq) Cd(OH)2(s) + 2 e- Eox = 0.806 V


Now plug this result back into the first set of redox reactions:
{NiO(OH)(s) + e + H+(aq) Ni(OH)2(s)
{Cd(s) + 2 OH (aq) Cd(OH)2(s) + 2 e

}2
} 1

Ered
Eox = 0.806 V

2 NiO(OH)(s) + Cd(s) + 2 H2O(l) Cd(OH)2(s) + 2 Ni(OH)2(s) Ecell 1.50 V


Ered = 1.50 V 0.806 V = 0.69 V

1147

Chapter 23: The Transition Elements


[II]

41.

[III]

[II]

(E) Fe3+(aq) + K4[F e(CN)6](aq) K F e [F e(CN)6](s) + 3 K+(aq)


-

[II]

[II]

Alternate formulation: 4Fe3+ + 3[F e(CN)6]4 (aq) + Fe4[F e(CN)6]3


[III]

42.

[II]

(E) K+(aq) + Fe2+(aq) + K3[Fe(CN)6](aq) Fe3+(aq) + K4[Fe(CN)6](aq)


[II]

[III]

[II]

Fe3+(aq) + K4[Fe(CN)6](aq) KFe [Fe(CN)6](s) + 3 K+(aq)

Group 11 Metals
43.

44.

(E) (a) Cu 2 + aq + H 2 g Cu s + 2H + aq
(b)

Au + aq + Fe 2+ aq Au s + Fe 3+ aq

(c)

2Cu 2+ aq + SO 2 g + 2 H 2 O(l) 2 Cu + aq + SO 4

aq + 4 H + aq

(M) In either case, the acid acts as an oxidizing agent and dissolves silver; the gold is
unaffected.
Oxidation:
{Ag s Ag + aq + e }
3

Reduction:

NO 3 aq + 4H + aq + 3e NO g + 2H 2 O (l)

Net:

3Ag s + NO3 aq + 4H + aq 3Ag + aq + NO g + 2H 2 O(l)

Oxidation:

{Ag s Ag + aq + e }

Reduction:

SO 4

Net:
45.

aq + 4H + aq + 2e SO2 g + 2H 2O(l)
2
2 Ag s + SO 4 aq + 4 H + aq 2 Ag + aq + SO 2 g + 2 H 2 O(l)
2

Cu 2+
(M) The Integrative Example showed K c = 1.2 106 =
or
2
Cu +
2

2+
6
+
Cu = 1.2 10 Cu
2
(a) When Cu + = 0.20 M, Cu 2+ = 1.2 106 0.20 = 4.8 104 M. This is an
impossibly high concentration. Thus Cu + = 0.20 M can never be achieved.

(b) When Cu + = 1.0 1010 M, Cu 2+ = 1.2 106 1.0 1010 = 1.2 1014 M . This is
an entirely reasonable (even though small) concentration; Cu + = 1.0 1010 M can
2

be maintained in solution.
46.

(M) Oxidation: {Cu(s) Cu2+ + 2 e


}2
Reduction: {O2(g) + 2 H2O(l) + 4 e 4 OH (aq) }1

Overall: 2 Cu(s) + O2(g) + 2 H2O(l) 2 Cu2+(aq) +4 OH (aq)


Note:

This produces an alkaline solution. CO2 dissolves in this alkaline solution


to produce carbonate ion.

1148

Chapter 23: The Transition Elements

Step(a): CO2(g) + OH (aq) HCO3 (aq)


Step(b): HCO3 (aq) + OH (aq) CO32 (aq) + H2O(l)
Total:

CO2(g) + 2 OH (aq) CO32 (aq) + H2O(l)

Combination of the reactions labeled "overall" and "total" gives the following result.
2 Cu(s) + O2(g) + H2O(l) + CO2(g) 2 Cu2+(aq) + 2 OH (aq) + CO32 (aq)
The ionic product of the resultant reaction combine in a precipitation reaction to form
2 Cu2+(aq) + 2 OH (aq) + CO32 (aq) Cu2(OH)2CO3 (s)
Group 12 Metals
47.

(E) Given: Hg2+/Hg reduction potential = 0.854 V and Hg22+/Hg reduction potential = 0.796 V
Using the additive nature of free energies and the fact that G = -nFE, we can determine the
2(0.854V) - 0.796V
= 0.912 V
Hg2+/Hg22+ potential as
1

48.

(M) G = -25,000 J mol-1 = -RTlnKeq = -(8.3145 J K-1 mol-1)(673 K)(lnKeq)

Keq = Kp = 87 atm-1 =

49.

1
PO2

Therefore, PO2 =

1
1
=
= 0.011 atm
KP
87

(M) (a) Estimate Kp for ZnO(s) + C(s) Zn(l) + CO(g) at 800 C (Note: Zn(l) boils at 907 C)

{2 C(s) + O2(g) 2 CO(g)} 1/2

G = ( 415 kJ) (1/2)

{2 ZnO(s) 2 Zn(l) + O2(g)}1/2

G = (+485 kJ) (1/2)

ZnO(s) + C(s) Zn(l) + CO(g)

G = 35 kJ

Use G = -RTlnKeq where T = 800 C, Keq = Kp


35 kJ mol-1 = -(8.3145 10-3 kJ K-1 mol-1)((273.15 + 800) K)(ln Kp)
lnKp = -3.9 or Kp = 0.02
(b)
50.

Kp = PCO = 0.02 Hence, PCO = 0.02 atm

(M) T = 298 K. Hence, log (PmmHg) =

0.05223 (61,960)
+ 8.118 = 2.742
298

PmmHg = 0.001811 mmHg

1149

Chapter 23: The Transition Elements

n
P

= [Hg] =
V RT

PV = nRT

1atm
)
760 mmHg
= 9.744 10 8 mol L 1

L atm
0.08206
(298K)
K mol

(0.001811mmHg)(

Next, convert to mg Hg m 3:
mol 1000 L 200.59 g Hg 1000 mg

3
[Hg] = 9.874 x 108

= 19.5 mg Hg m

3
L m 1mol Hg 1g Hg

(This is approximately 400 times greater than the permissible level of 0.05 mg Hg m 3)
51.

(M) We must calculate the wavelength of light absorbed in order to promote an electron
across each band gap.

First, a few relationships. Emole = N A Ephoton

Ephoton = hv

Then, some algebra. Emole = N A Ephoton = N A hv = N A hc/


For ZnO, =
=

For CdS, =

6.022 10

23

c = v or v = c/

or

34

= N A hc/Emole
1

mol 6.626 10 J s 2.998 10 m s


109 nm

290 103 J mol1


1m

1.196 108 J mol1 nm


= 413 nm
290 103 J mol1

violet light

1.196 108 J mol1 nm


= 479 nm blue light
250 103 J mol1

The blue light absorbed by CdS is subtracted from the white light incident on the surface
of the solid. The remaining reflected light is yellow in this case. When the violet light is
subtracted from the white light incident on the ZnO surface, the reflected light appears
white.

52.

(D) The color that we see is the complementary color to the color absorbed. The color
absorbed, in turn, is determined by the energy separation of the band gap. If the
wavelength for the absorbed color is short, the energy separation for the band gap is large.

The yellow color of CdS means that the complementary color, violet, is absorbed. Since
violet light has a quite short wavelength (about 410 nm), CdS must have a very large band
gap energetically.
HgS is red, meaning that the color absorbed is green, which has a moderate wavelength
(about 520 nm). HgS must have a band gap of intermediate energy.
CdSe is black, meaning that visible light of all wavelengths and thus all energies in the
visible region are absorbed. This would occur if CdSe has a very small band gap, smaller
than that of least energetic red light (about 650 nm).
1150

Chapter 23: The Transition Elements

INTEGRATIVE AND ADVANCED EXERCISES


53. (M) There are two reasons why Au is soluble in aqua regia while Ag is not. First, Ag+, the
oxidation product, forms a very insoluble chloride, AgCl, which probably adheres to the
surface of the metal and prevents further reaction. AuCl3 is not noted as being an insoluble
chloride. Second, gold(III) forms a very stable complex ion with chloride ion, [AuCl4]. This
complex ion is much more stable than the corresponding dichloroargentate ion, [AgCl2].
54. (E) Sc and Ti metals form carbides in the presence of carbon (coke). Thus, reduction of
their oxides using carbon is avoided.
55. (M) Both tin and zinc are toxic metals in high concentrations. Tin plated iron is more
desirable than zinc plated (galvanized) iron. The reason for this is that zinc is a very
reactive metal, especially in the presence of acidic foods. Tin, on the other hand, is much
less reactive ( ESn 2+ /Sn = -0.137 V vs. E Zn 2+ /Zn = -0.763 V). As well, tin is more malleable

and more easily prepared in pure form (free of oxide).


56.
(M)

Oxidation :

{Cu(s)
Cu 2 (aq) 2 e } 2

Reduction :

O 2 (g) 2 H 2 O(l) 4 e
4 OH (aq)

Net :

2 Cu(s) O 2 (g) 2 H 2 O(l)


2 Cu 2 (aq) 4 OH (aq)

This oxidation-reduction reaction produces an alkaline solution. SO3(g) dissolves in this alkaline
solution to produce hydrogen sulfate ion in an acid-base reaction.

Step (a) :

HSO 4 (aq)
SO 3 (g) OH (aq)

Step (b) :

SO 4 (aq) H 2 O(l )
HSO 4 (aq) OH (aq)

Total :

SO 3 (g) 2 OH (aq)
SO 4 (aq) H 2 O(l)

The combination of the reactions labeled Net: and Total: gives the following result.

2 Cu(s) O 2 (g) H 2 O(l) SO3 (g)


2 Cu 2 (aq) 2 OH (aq) SO 4 2 (aq)
The ionic products of this resultant reaction combine in a precipitation reaction to form
2
Cu 2 (OH) 2 SO 4 (s)
Cu2(OH)2SO4(s). Thus, 2 Cu 2 (aq) 2 OH (aq) SO 4 (aq)

57. (M) The noble gas formalism requires that the number of valence electrons possessed by the
metal atom plus the number of sigma electrons be equal to the number of electrons in the
succeeding noble gas atom.
(a) Mo(CO)6 ; Mo has 42 electrons, 6 CO contribute another 12 for 54, which is the number
of electrons in Xe

1151

Chapter 23: The Transition Elements

(b) Os(CO)5 ; Os has 76 electrons, 5 CO contribute another 10 for 86, which is the number
of electrons in Rn
(c) Re(CO)5-; Re anion has 76 electrons, 5 CO contribute another 10 for 86, which is the
number of electrons in Rn
(d) The trigonal bipyramidal shape of nickel and iron carbonyls does not fit well in
crystalline lattices, either because of its symmetry or repulsions with its neighbors and,
consequently, these five-coordinate carbonyls are liquids at room temperature.
Compare this to octahedral complexes (Cr(CO)6 and others), which are solids because
they fit well into these lattices. Weak intermolecular attractions in the low molecular
mass, symmetrical nickel and iron carbonyls result in the liquid state at room
temperature. Because of the two metal atoms in the higher molecular mass, less
symmetrical cobalt carbonyl molecules, stronger intermolecular attractions lead to the
solid state.
(e) This compound would be an ionic, salt-like material consisting of Na+ and V(CO)6- ions.
58. (M) (a) Breaks occur at the melting point and boiling point due to changes in the states of
the metals (solid liquid gas).
(b) Slopes of these lines become more positive as the temperature increases due to the sign of
S for these reactions. The slope should be equal to -S, where S is a negative
number in these cases that becomes more negative with a change in phase (higher
temperature).
(c) The break at the boiling point is sharper than the break at the melting point because
Sfusion <<Svaporization.
59.

(M) Oxidation :

2 I (aq)
I 2 (s) 2 e

Reduction:{Cu 2 (aq) e
Cu (aq)}

E 0.535 V
2

E 0.159 V

Net:
Cu 2 (aq) 2 I (aq)
2 Cu (aq) I2 (s) E cell 0.376 V
G nFE RT ln K
ln K

nFE 2 mol e 96485 C/mol e 0.376 V

29.3
RT
8.3145 J mol1 K 1 298.15 K

Redox: Cu 2 (aq) 4I (aq)


2 Cu (aq) I 2 (s) 2 I (aq)
Precipitation: {Cu (aq) I (aq)
CuI(s)}
Total:
K

K e29.3 2 1013

K redox 2 1013

1/ K sp 2 1/(1.1 1012 ) 2

Cu 2 (aq) 4 I (aq)
2 CuI s I 2 (s)

K redox
2 1013

2 1011
12)2
K sp 2
(1.1 10

n2

Clearly this reaction will occur as written.

I2 and I- form I3- in aqueous solution. So, adding an additional mole of I- to the last
reaction yields:
Cu 2 (aq) 5 I (aq)
2 CuIs I 3 (s)

1152

Chapter 23: The Transition Elements

60. (D) A detailed calculation would involve determining the final concentrations of all
species. But we can get approximate values of the gold-containing ions by determining
values of the equilibrium constants for the reactions involved. First, we determine the value
of the equilibrium constant for the disproportionation of Au+(aq). To accomplish this, find
the value of Eo for the couple Au+(aq)|Au(s).
Au (aq)
Au 3 (aq) 2 e

Oxidation

E 1.36 V

Reduction:

{Au (aq) e
Au(s)} 2

E 1.83 V

Net:

3Au (aq)
Au 3 (aq) 2 Au(s)

Ecell
0.47 V

ln K

nFE 2 mol e 96485 C/mol e 0.47 V

36.6
RT
8.3145 J mol1 K 1 298.15 K

K e36.6 8 1015

Then we determine the value of the equilibrium constant for dissolving and disproportionation.
Disproportionation :

3 Au (aq)
Au 3 (aq) 2 Au(s) K disp 8 1015

Dissolving :

{AuCl(s)
Au (aq) Cl (aq)} 3

Net :

3 AuCl(s)
Au 3 (aq) 2 Au(s) 3 Cl (aq)

K K disp K sp 8 10 (2.0 10
3

15

13 3

) 6.4 10

23

K sp (2.0 10 13 ) 3
K

[Au ][Cl ] ( x)(3 x)3 27 x 4

6.4 1023
1 106 M [Au 3 ]
27

This is a significant amount of decomposition, particularly when compared with


[Au+] = 4.5 107 M, which is the concentration present in saturated AuCl, assuming no
disproportionation.
61. (M) (a)

AgO(s) 2 H (aq)
Ag 2 (aq) H 2 O(l)

Dissolution:

Oxidation :

2 H 2 O(l)
O 2 (g) 4 H (aq) 4 e
2

E 1.229 V

Reduction :

{Ag (aq) e
Ag (aq)}

E 1.98 V

Net :

2 H 2 O(l) 4 Ag 2 (aq)
O 2 (g) 4 H (aq) 4 Ag (aq)

(b) E ocell 1.229 V 1.98 V 0.75 V spontaneous since E ocell > 0.


62. (M)

Association:
Elimination:

2 HCrO 4 (aq)
2 H (aq) 2 CrO 4 2 (aq)
Cr2O7 2 (aq) H 2 O(l)
2 HCrO 4 (aq)

1/ K a 2 1/ (3.2 107 ) 2
K

Cr2 O7 2 (aq) H 2 O(l) K c 3.2 1014


2 H (aq) 2 CrO 4 2 (aq)
K
K
K c 3.2 1014 2
K 3.2 1014 (3.2 107 ) 2 33
Ka
(3.2 107 ) 2
Eqn. (23.18)

1153

Chapter 23: The Transition Elements

63. (D) The presence of both acetate ion and acetic acid establishes a buffer and fixes the pH of
the solution. This, in turn, fixes [CrO42]. We then can determine the concentration of each
of the cations that can coexist with this [CrO42] before precipitation occurs. First we
determine [H3O+], with the aid of the Henderson-Hasselbalch equation.

pH pK a log

[C 2 H 3 O 2 ]
1.0 M
log (1.8 105 ) log
4.74
[HC2 H3 O2 ]
1.0 M

[H 3 O ] 104.74 1.8 105 M


K c 3.2 1014

[Cr2 O7 2 ]
0.0010 M
3.1 106

[CrO 4 2 ]2 [H3 O ]2 [CrO 4 2 ]2 (1.8 105 ) 2 [CrO 4 2 ]2

3.1 106
9.8 105 M
14
3.2 10
K sp
1.2 1010

1.2 106 M
2
5
[CrO4 ] 9.8 10

[CrO 4 2 ]
[Ba 2 ]max

2.2 105
0.22 M
9.8 105
7.1 104

7.2 M
9.8 105

[Sr 2 ]max
[Ca 2 ]max

Each cation is initially present at 0.10 M. Neither strontium ion nor calcium ion will
precipitate, while BaCrO4 will precipitate until [Ba2+] has declined to far less than 0.1% of
its original value. Thus, barium ion is effectively separated from the other two cations by
chromate ion precipitation under these conditions.
64. (D) The equations are balanced with the ion-electron method. Oxalic acid is oxidized in each
case.
Oxidation: H 2 C 2 O 4 (aq)
2 H (aq) 2 CO 2 (g) 2 e
Reduction:MnO 2 (s) 4 H (aq) 2 e
Mn 2 (aq) 2 H 2 O(l)
Net: H 2 C2 O 4 (aq) MnO 2 (s) 2 H (aq)
Mn 2 (aq) 2 CO 2 (g) 2 H 2 O(l )
Oxidation:{H 2 C 2 O 4 (aq)
2 H (aq) 2

CO 2 (g) 2 e

} 5

Reduction: {MnO 4 (aq) 8 H (aq) 5 e


Mn (aq) 4 H 2 O(l) } 2
Net: 5 H 2 C 2 O 4 (aq) 2 MnO 4 (aq) 6 H (aq)
2 Mn 2 (aq) 10 CO 2 (g) 8 H 2 O(l)
We then determine the mass of the excess oxalic acid.

0.1000 mol MnO 4


5 mol H 2 C 2 O 4
mass H 2 C 2 O 4 2H 2 O 0.03006 L

1 L soln
2 mol MnO 4

126.07 g H 2 C 2 O 4 2H 2 O
0.9474 g H 2 C 2 O 4 2H 2 O
1 mol H 2 C 2 O 4 2H 2 O

1154

Chapter 23: The Transition Elements

Thus, the mass of oxalic acid that reacted with MnO2 is 1.651 g 0.9474 g = 0.704 g
H2C2O42H2O. Now we can determine the mass of MnO2 in the ore.
mass MnO 2 0.704 g H 2 C2 O 4 2H 2 O

86.94 g MnO 2
0.485 g MnO 2
1 mol MnO 2

1 mol H 2 C 2 O 4 .2H 2 O
1 mol MnO 2

126.07 g H 2 C2 O 4 2H 2 O 1 mol H 2 C2 O 4
%MnO 2

0.485 g MnO 2
100% 82.3%
0.589 g ore

65. (D) (a)


We consider reaction with 1.00 millimoles of Fe2+. In each case, we need the
balanced chemical equation of the redox reaction.
2

Cr2 O 7 (aq) 14 H (aq) 6 Fe 2 (aq)


2 Cr 3 (aq) 7 H 2 O(l) 6 Fe 3 (aq)
2
titrant
1 mmol Cr2 O 7
1 mL solution
2
1.00
mmol
Fe

1.67 mL soln
2
2
volume
6 mmol Fe
0.1000 mmol Cr2 O 7

MnO 4 (aq) 8 H (aq) 5 Fe 2 (aq)


Mn 2 (aq) 4 H 2 O 5 Fe 3 (aq)

titrant
1 mmol MnO 4
1 mL solution
3
volume 1.00 mmol Fe 5 mmol Fe 2 0.1000 mmol MnO 2.00 mL soln
4

More of the 0.1000 M MnO4 solution would be required.


(b) We use the reaction of each with Fe2+ to find the equivalence between them.
VMnO 24.50 mL
4

0.1000 mmol Cr2 O7 2


1 mmol MnO 4
6 mmol Fe 2

1 mL soln
1 mmol Cr2 O7 2
5 mmol Fe 2

1 mL soln
29.40 mL of 0.1000 mmol MnO 4

0.1000 mmol MnO 4

66. (M) A high oxidation state of a metal can only be stabilized by an anion of an element that is
highly electronegative. Fluorine and oxygen are the two most electronegative elements in
the periodic table and thus should be most effective at stabilizing a high oxidation state of a
metal.
67. (D) The precipitation reaction of dichromate ion permits us to determine from the formula of
barium chromate the amount of chromium present, while the redox reaction of
permanganate ion permits us to determine the amount of manganese present in the 250.0 mL
solution. The 15.95 ml volume of Fe2+ titrant assumes (contrary to what the problem
implies) that the chromate has been removed by precipitation. Ba(MnO4)2 is quite water

soluble, so [ MnO 4 ] should not be affected.

1155

Chapter 23: The Transition Elements

Equation:

MnO 4 (aq) 8 H (aq) 5 Fe 2 (aq)


Mn 2 (aq) 4 H 2O 5 Fe3 (aq)

mass of Cr 250.0 mL soln

0.549 g BaCrO 4
1 mol BaCrO 4
1 mol Cr
52.00 g Cr

10.00 mL sample 253.3 g BaCrO4 1 mol BaCrO 4 1 mol Cr

mass of Cr 2.82 g Cr
equation:

Cr2 O7 2- 14 H 6 Fe 2 2Cr 3 7 H 2 O 6 Fe3

volume of titrant to reduce Cr2 O 7 2- 2.82 g Cr

10 ml 1 mol Cr 3 6 mol Fe 2

250 ml 52.00 g Cr 1 mol Cr2 O7 2-

1 mol Cr2 O7 21 L titrant


1000 mL

86.78 ml Fe2 titrant


3
2
1L
2 mol Cr
0.0750 mol Fe
Now the volume of titrant to reduce both MnO 4 - and Cr2 O 7 2- must be (15.95 86.78) mL
Volume of titrant 102.73 mL.
Not just 15.95 mL, which must be the volume of titrant required for MnO 4 alone.
15.95 mL titrant 0.0750 mmol Fe2 1 mmol MnO 4

10.00 mL sample
1 mL titrant
5 mmol Fe 2
1 mmol Mn
54.94 mg Mn
1 g Mn

0.3286 Mn

1 mmol Mn 1000 mg Mn
1 mmol MnO 4

mass Mn 250.0 mL soln

%Mn

0.3286 g Mn
2.82 g Cr
100% 3.286% Mn %Cr
100% 28.2% Cr
10.000 g steel
10.000 g steel

68. (M) (a)

We use the technique of Chapter 3 to determine the empirical formula of nickel

dimethylglyoximate.
1 mol Ni
0.3461 mol Ni
58.69 g Ni
1 mol C
33.26 g C
2.769 mol C
12.011 g C
20.31 g Ni

4.88 g H

1 mol H

1.008 g H

4.84 mol H

1 mol O
1.384 mol O
15.999 g O
1 mol N
19.39 g N
1.384 mol N
14.007 g N
22.15 g O

0.3461
1.000 mol Ni
0.3461
8.001 mol C
0.3461
14.0 mol H

0.3461
3.999 mol O
0.3461
3.999 mol N

The empirical formula of nickel dimethylglyoximate (NiDMG) is NiC8H14O4N4, with


an empirical molar mass of 288.91 g/mol
(b) mass of Ni 250.0 mL

0.104 g NiDMG
1 mol NiDMG
58.69 g Ni
1 mol Ni

10.00 mL
288.91 g NiDMG 1 mol NiDMG 1 mol Ni

1156

Chapter 23: The Transition Elements

0.528 g Ni
0.528 g Ni
% Ni in steel
100% 3.52%
15.020 g steel
A

69. (M)

look

at

Appendix

indicates

that

Cr(OH)3, K sp 6.3 10 31 ;

Zn(OH)2, K sp 1.2 10 17 ; Fe(OH)3, K sp 4 10 38 ; and Ni(OH)2, K sp 2.0 10 15 ; all are


expected to form. But in excess NaOH, [Cr(OH)4], K f 8 10 29 , which probably is green
in color; and [Zn(OH)4]2, K f 4.6 1017 , also will form. (i.e., their hydroxides will
dissolve). The lack of color in the solution indicates that Cr3+ is not present. The presence of
a hydroxide precipitate indicates that Ni2+ and Fe3+ may be present. Because Ni2+ forms a
complex ion with NH3, [Ni(NH3)6]2+, K f 5.5 10 8 , and Fe3+ does not, the lack of a second
precipitate indicates that Fe3+ is absent. The fact that there was a hydroxide precipitate
indicates that Ni2+ is present. We are sure that Ni2+ is present and that Fe2+ and Cr3+ are
absent, but we are uncertain about the presence or absence of Zn2+.
70.

(M) First calculate concentration of Hg(NO3)2 solution:


? mol NaCl = 2.00 103 mL 0.0108 mol L1 = 2.16 105 mol NaCl
1
? mol HgCl2 = 2.16 105 mol NaCl = 1.08 105 mol
2
C = 1.08 105 mol/1.12 103 L = 9.64 103 mol L1
Next, calculate amount of Cl in the serum sample:
? mol Cl = 1.23 103 L 9.64 103 mol Hg2+ L1 2 mol Cl/1 mol Hg2+
= 2.37 105 mol Cl
= 0.0237 mmol
This amount of Cl came from a 0.500 mL serum sample, so the concentration of Cl in
mmol L1 is C = 0.0237 mmol/0.500 103 L = 47 mmol L1.

The concentration is smaller than the lower limit of the normal range.
71. (M)
(a)

(b)

(c)
O

O
Hg

72.

(M)

O
Mn

Hg

O
Mn

Os
O

O
O

(7)(1.60 1019 C)
4500 C mm 3
9
3
(4/3)(39 10 mm)

This value is more than 4 times the value given in Table 21.4 for Be2+ (1108 C mm3).
We know that there is significant covalent bonding in beryllium compounds. We expect

1157

Chapter 23: The Transition Elements

the bonding in Mn2O7 to be primarily covalent. With such a large charge density, a Mn7+ ion
would be very strongly polarizing, drawing electron density away from surrounding anions and
leading to bonds with primarily covalent character.
1
73.
(M) ? Ti per unit cell = Ti per corner 8 corners per cell = 1 Ti
8
? Ni per unit cell = 1
The empirical formula is NiTi. The % Ti by mass is 100 47.88/(47.88 + 63.55) = 45%

FEATURE PROBLEMS
74.

(D) (a) If ngas = 0, then S ~ 0 and G is essentially independent of temperature

(C(s) + O2(g) CO2(g))


If ngas > 0, then S > 0 and G will become more negative with increasing
temperature, hence the graph has a negative slope (2 C(s) + O2(g) 2 CO (g)).
If ngas < 0, then S < 0 and G will become more positive with increasing
temperature, hence the graph has a positive slope (2 CO(g) + O2(g) 2 CO2 (g).
(b)

The additional blast furnace reaction, C(s) + CO2(g) 2 CO(g)), has


H = [2 110.5 kJ] [ 393.5 kJ + 0 kJ] = 172.5 kJ and
S = [2 197.7 J K-1] [1 5.74 J K-1 + 213.7 J K-1] = 176.0 J K-1
It can be obtained by adding reaction (b) to the reverse of reaction (c) (both appear
in the provided figure)
C(s) + O2(g) CO2(g)
Reaction (b)
2CO2(s) 2CO(g) + O2(g) Reverse of Reaction (c)
Net: C(s) + CO2(g) 2 CO(g) (Additional Blast Furnace Reaction)

Consequently, the plot of G for the net reaction as a function of temperature will
be a straight line with a slope of [{S (Rxn b)} {S (Rxn c)}] (in kJ/K) and a
y-intercept of [{H (Rxn b)} {H (Rxn c)}] (in kJ).
Since Ho (Rxn b) = 393.5 kJ, Ho (Rxn c) = 566 kJ, So (Rxn b) = 2.9 J/K and
So (Rxn c) = 173.1 J/K, the plot of G vs. T for the reaction
C(s) + CO2(g) 2 CO(g) will follow the equation y 0.176 x 172.5
From the graph, we can see that the difference in G (line b line c at 1000 C) is
~ 40 kJ/mol. Kp is readily calculated using this value of G.
G = -RTlnKp = -40 kJ = (8.3145 10-3 kJ K-1 mol-1)( 1273 K)(ln Kp)
lnKp = 3.8 Hence, Kp = 44
The equilibrium partial pressure for CO(g) is then determined by using the
Kp expression:
1158

Chapter 23: The Transition Elements

P
K CO
p

PCO

(PCO2 )

44

(0.25 atm)

Hence, (PCO)2 = 11 and PCO = 3.3 atm or 3 atm.

Alternatively, we can determine the partial pressure for CO2 at 1000 C via the calculated
H and S values for the reaction C(s) + CO2(g) 2 CO(g) to find G at 1000 C ,
and ultimately Kp with the relationship G = -RTlnKp (here we are making the
assumption that H and S are relatively constant over the temperature range 298 K to
1273 K). The calculated values of H and S (using Appendix D) are given below:
H = [2 110.5 kJ] [ 393.5 kJ + 0 kJ] = 172.5 kJ
S = [2 197.7 J K-1] [1 5.74 J K-1 + 213.7 J K-1] = 176.0 J K-1
To find G at 1000oC, we simply plug x =1273 K into the straight-line equation we
developed above and solve for y (G).
So, y 0.176(1273K) 172.5 ; y 51.5 kJ
Next we need to calculate the Kp for the reaction at 1000oC.

G = -RTlnKp = -51.5 kJ = -(8.3145 10-3 kJ K-1 mol-1)( 1273 K)(ln Kp)


lnKp = 4.87 Hence, Kp = 1.3 102
The equilibrium PCO(g) is then determined by using the Kp expression:

P
K CO
p

75.

(PCO2 )

PCO

(0.25 atm)

Hence, (PCO)2 = 32.5 atm and PCO = 5.7 atm

(M) (a) The amphoteric cations are Al3+, Cr3+, and Zn2+.
-

Cr3+(aq) + 4OH (aq) [Cr(OH)4] (aq)


Al3+(aq) + 4OH (aq) [ Al(OH)4] (aq)
-

Zn2+(aq) + 4OH (aq) [Zn(OH)4]2 (aq)


-

Fe3+(aq) + 3OH (aq) Fe(OH)3(s)


-

Ni2+(aq) + 2OH (aq) Ni(OH)2(s)


-

Co2+(aq) + 2OH (aq) Co(OH)2(s)


(b)

Of the three hydroxide precipitates, only Co2+ is easily oxidized:


(refer to the Standard Reduction Potential table in Appendix D).
2 Co(OH)2(s) + H2O2(aq) 2 Co(OH)3(s)

(c)

We know that the chromate ion is yellow. Thus,


-

[Cr(OH)4] (aq) + 3/2 H2O2(aq) + OH (aq) CrO42 (aq, YELLOW) + 4 H2O(l)

1159

Chapter 23: The Transition Elements

(d)

Co3+ is reduced to Co2+ by the H2O2 in solution. The other hydroxides simply
dissolve in strong acid:
+

(i) Co(OH)3(s) + 3H (aq) Co3+(aq) + 3H2O(l)

(e)

(ii)

2 Co3+(aq) + 2 Cl-(aq) 2 Co2+(aq) + Cl2(g)

(iii)

Fe(OH)3(s) + 3 H+(aq) Fe3+(aq) + 3 H2O(l)

(iv)

Ni(OH)2(s) + 2 H (aq) Ni2+(aq) + 2 H2O(l)

The Fe3+(aq) ions in the presence of concentrated ammonia(6 M) form an insoluble


precipitate with the hydroxide ions generated by the ammonia hydrolysis reaction:
+

NH3(aq) + H2O(l)

NH4 (aq) + OH (aq)

Ksp Fe(OH)3 = 4 10-38


Fe3+(aq) + 3 OH (aq)

Fe(OH)3(s);

Both Co3+ and Ni2+ form soluble complex ions with ammonia ligands rather than
hydroxide precipitates.

SELF-ASSESSMENT EXERCISES
76.

(E) (a) A key feature of ferromagnetism is that in the solid state, the metal atoms are
thought to be grouped together into small regions called domainscontaining rather
large numbers of atoms.
(b) Flotation is a process used to determine metal concentration.
(c) Leaching is the process by which metal ions are extracted (leached) from the ore by a
liquid. Leaching agents include water, acids, bases, and salt solutions. Oxidation
reduction reactions may also be involved.
(d) Mercury alloys, called amalgams, are commonly made with most metals, and some of
these amalgams are of commercial importance.

77.

(E) (a) In the series of elements in which the 4f subshell is filled, atomic radii decrease
somewhat. This phenomenon occurs in the lanthanide series ( Z=58 to 71) and is called
the lanthanide contraction.
(b) Zone melting (or zone refining or floating zone process) is a group of similar methods
of purifying crystals, in which a narrow region of a crystal is molten, and this molten
zone is moved along the crystal (in practice, the crystal is pulled through the heater). The
molten region melts impure solid at its forward edge and leaves a wake of purer material
solidified behind it as it moves through the ingot. The impurities concentrate in the melt,
and are moved to one end of the ingot.
(c) Basic oxygen process is a steelmaking method in which pure oxygen is blown into a
bath of molten blast-furnace iron and scrap. The oxygen initiates a series of intensively
exothermic (heat-releasing) reactions, including the oxidation of such impurities as
carbon, silicon, phosphorus, and manganese.

1160

Chapter 23: The Transition Elements

(d) Slag formation is used to remove impurities from ores.


78.

(E) (a) Ferromagnetism is the basic mechanism by which certain materials (such as iron)
form permanent magnets, or are attracted to magnets. Paramagnetism is a form of
magnetism which occurs only in the presence of an externally applied magnetic field.
Paramagnetic materials are also attracted to magnetic fields.
(b) An ore is roasted (heated to a high temperature) to convert a metal
compound to its oxide, which can then be reduced. The oxidation number of a metal
decreases as a result of reduction.
(c) Hydrometallurgy is part of the field of extractive metallurgy involving the use of
aqueous chemistry for the recovery of metals from ores, concentrates, and recycled or
residual materials. Pyrometallurgy is a branch of extractive metallurgy. It consists of the
thermal treatment of minerals and metallurgical ores and concentrates to bring about
physical and chemical transformations in the materials to enable recovery of valuable
metals.
(d) Chromates are the salts that contain CrO42- anions. Dichromates, on the other hand,
contain Cr2O72- anions. In both compounds chromium is in +6 oxidation state.

79.

(E) (a) Pig iron is impure iron (95% Fe) formed in the reduction of iron ore in a blast
furnace.
(b) Ferromanganese is an iron-manganese alloy formed by the reduction of a
mixture of iron and manganese oxides.
(c) Chromite ore, Fe(CrO2)2 is the principal chromium ore.
(d) Brass is an allow of Zn and Cu with small amounts of Sn, Pb, and Fe.
(e) Aqua regia is a mixture of HCl(aq) and HNO3(aq) that dissolves inactive metals by a
combination of oxidation and complex ion formation.
(f) Blister copper, formed in the
reduction of a mixture of Cu2O(s) and Cu2S(s), is
impure Cu(s) containing SO2(g).
(g) Stainless steel is an iron alloy with varying quantities of metals such as Cr, Mn,
and Ni, and a small and carefully controlled percentage of carbon.

80.

(E) (c), (f), and (g).

81.

(E) (b)

82.

(E) (d)

83.

(E) (a)

84.

(E) (d)

85.

(E) (c) and (e)

86.

(M) CrO3(s), (b) potassium manganate, (c) chromium carbonyl, (d) BaCr2O7, (e)
lanthanum(III) sulfate nonahydrate, (f) Au(CN)33H2O.

1161

Chapter 23: The Transition Elements

87.

(M) (a) 2Fe 2 S3 (s)+3O 2 (g)+6H 2O(l) 4Fe(OH)3 (s)+6S(s)


(b) 2Mn 2+ (aq)+8H 2 O(l)+5S2 O 2-8 (aq) 2MnO-4 (aq)+16H + (aq)+10SO 2-4 (aq)
(c) 4Ag(s)+8CN - (aq)+O 2 (g)+2H 2O(l) 4[Ag(CN 2 ]- (aq)+4OH - (aq)

88.

(M) Atoms of Zn, Cd and Hg have configurations of 4 s 2 3d 10 , 5 s 2 4 d 10 , and


6 s 2 4 f 14 5 d 10 , respectively. One the ns 2 electrons participate in bonding, and in this
regard Zn, Cd, and Hg resemble the group 2 elements.

89.

(M) HNO3 is the oxidizing agent for oxidizing the metal to Au3+ but Au3+ must be
stabilized in solution. In aqua regia, Cl- ions combine with Au3+ to form [AuCl4]-, which
is stable in solution.

90.

(M) The Fe3+ ion forms a complex ion, Fe(H2O)63+, in aqueous solution. The complex
behaves as a weak monoprotic acid in solution. See Equation (23.36).

1162